Ionically interacting polymers

ABSTRACT

Reversibly cross-linked, thermoplastic, normally solid polymer salt compositions have been prepared by copolymerizing a prepolymer of a carboxyl containing polyolefin, having 2 to 50 mole percent carboxylic acid groups, and about 10 to 100 mole percent of its carboxyl groups neutralized with an amino vinyl monomer such as an alkylaminoalkyl acrylate, an alkylaminoalkyl methacrylate, or an amino substituted styrene with a vinyl monomer such as an alkyl acrylate, an alkyl methacrylate, acrylamide, methacrylamide, styrene, alkyl substituted styrenes, vinyl chloride, vinyl esters containing from three to 20 carbon atoms or vinyl alkyl ethers containing from three to 20 carbon atoms. These polymer salt compositions are particularly useful in that they exhibit a high degree of adhesion to plasticized vinyl chloride resins, unlike most other commonly known adhesives, as well as other substrates.

United States Patent Chow et a1.

[ Feb. 8, 1972 [54] IONICALLY INTERACTING POLYMERS [72] Inventors:Sui-Wu Chow; Walter H. Smarook, both [21] Appl. No.: 49,568

Related US. Application Data [63] Continuation-impart of Ser. No.669,291, Sept. 20,

1967, abandoned.

[52] US. Cl ..l61/190,117/l23,117/124, 117/127, 117/128.4, 117/132,117/138.8, 117/143, 117/147,117/152,117/161,16l/203,161/204,

3,325,561 6/1967 Grillo et al ..260/857 3,337,517 8/1967 Anspon..260/86,7 3,388,186 6/1968 Kray et al. .L ..260/857 PrimaryExaminer-Joseph L. Schofer Assistant Examiner-A. Holler Attorney-Paul A.Rose, Aldo John Cozzi and Bernard Francis Crowe [57] ABSTRACT Reversiblycross-linked, thermoplastic, normally solid polymer salt compositionshave been prepared by copolymerizing a prepolymer of a carboxylcontaining polyolefin, having 2 to 50 mole percent carboxylic acidgroups, and about 10 to 100 mole percent of its carboxyl groupsneutralized with an amino vinyl monomer such as an alkylaminoalkylacrylate, an alkylaminoalkyl methacrylate, or an amino substitutedstyrene with a vinyl monomer such as an alkyl acrylate, an alkylmethacrylate, acrylamide, methacrylamide, styrene, alkyl substitutedstyrenes, vinyl chloride, vinyl esters containing from three to 20carbon atoms or vinyl alkyl ethers containing from three to 20 carbonatoms.

These polymer salt compositions are particularly useful in that theyexhibit a high degree of adhesion to plasticized vinyl chloride resins,unlike most other commonly known adhesives, as well as other substrates.

14 Claims, No Drawings IONICALLY INTERACTING POLYMERS This is acontinuation-in-part of Ser. No. 669,291 filed Sept. 20, 1967, nowabandoned.

This invention relates to reversibly cross-linked, thermoplasticnormally solid polymer salt compositions of a carboxyl containingpolyolefin which had been neutralized with an amino vinyl monomerprepolymer copolymerized with a vinyl comonomer.

Despite the expanding use of vinyl resins, that is, homopolymers orcopolymer of vinyl chloride in the form of films, sheets, structuralforms, and other applications, the lack of suitable adhesives forbonding vinyl resins to other materials has seriously curtailed theirutilization in many areas where they would otherwise be suitable. Thislack of adhesion is aggravated by the fact that most vinyl resinscontain a plasticizer such as dioctyl phthalate which often migrates tothe surface of the vinyl resin and further reduces adhesion.

It has now been found that a new class of polymers that is, ionicallyinteracting polymers are uniquely useful for bonding vinyl chlorideresins and other substrates to themselves as well as to othersubstrates. These ionically interacting polymers are reversiblycross-linked, thermoplastic, normally solid polymer salt compositionscomprising:

A. about 20 to 80 percent by weight of a prepolymer of a carboxylcontaining polyolefin having from 2 to 50 mole percent carboxyl groupsand about to 100 mole percent of said carboxyl groups neutralized withan amino vinyl monomer selected from the class consisting ofalkylaminoalkyl acrylates having from three to 13 carbon atoms in theacrylate moiety, alkylaminoalkyl methacrylates having from four to 13carbon atoms in the methacrylate moiety, and amino substituted styrenehaving the structural formula:

wherein q is an integer having values of from 0 to l, R is a divalentaliphatic radical having from one to six carbon atoms, and each of R andR is a radical selected from the group consisting of hydrogen and alkylgroups having from one to four carbon atoms, said prepolymer reactionproduct being copolymerized with:

B. about 80 to percent by weight of a vinyl monomer selected from theclass consisting of alkyl acrylates, alkyl methacrylates, acrylamide,methacrylamide, styrene, alkyl substituted styrenes having one to 16carbon atoms in the alkyl group, vinyl chloride, vinyl esters containingfrom about three to 20 carbon atoms and vinyl alkyl ethers containingfrom about three to 20 carbon atoms.

The polymer salt compositions of this invention not only exhibitexcellent adhesion to vinyl resins but also to other substrates such asmetals, as for example, aluminum, steel, galvanized iron, zinc, tin,copper, and the like, siliceous materials such as glass and the like,cellulosic materials such as wood, paper, and the like, vinylidenechloride polymers, thermoplastic polyhydroxy ethers, polystyrenes andrubbermodified styrene polymers, Dynel, that is, a modacrylic syntheticfiber made by the copolymerization of 40 percent acrylonitrile and 60percent vinyl chloride, polyurethanes, paperlike materials formed fromolefin polymer compositions such as those disclosed in US. Pat. No.3,234,313, Belgian Pat. Nos. 6,719 published Dec. 16, 1964, 27,296published Feb. 4, 1966 and 27,600 published May 3, 1966, and the like.

The degree of neutralization required for optimum adhesion of thepolymer salt compositions of this invention varies with the particularsubstrate or substrates bonded therewith. For example in the specificcase where an ethylene-acrylic acid copolymer containing 18 percent byweight copolymerized therein was neutralized with varying amounts ofdimethylaminoethyl methacrylate ranging from ratios of moles of thelatter to moles of carboxyl in the copolymer of 0.1 to 1.0 where theresultant neutralized products or prepolymers were then copolymerizedwith methyl methacrylate, the adhesion values with vinyl-aluminumlaminates was 'quite different from those with polyethylene-aluminumlaminates. While adhesion to vinyl resins increased by increasing thecontent of both dimethylaminoethyl and methyl methacrylate; adhesion topolyethylene decreased. Thus it was found that for this particularpolymer salt system it was preferred to use a prepolymer having about 15to 30 percent of the carboxyl groups neutralized for optimum adhesion topolyethylene.

While about 20 to percent by weight of prepolymer with about 80 to 20percent by weight of vinyl monomer can be used in the practice of thisinvention, it is preferred to use about 40 to 60 percent by weight ofthe former and about 60 to 40 percent by weight of the latter.

Although not essential, it is preferred to employ as the carboxylcontaining polyolefins of this invention interpolymers of alpha-olefinshaving the general formula:

where R is selected from the group consisting of hydrogen and alkylradicals having up to about 10 carbon atoms, the olefin content of saidinterpolymer being at least 50 mole percent of the total interpolymerand interpolymerized therewith an a, B-ethylenically unsaturatedcarboxylic acid having 1 or more carboxyl groups, said unsaturatedcarboxylic acid constituting up to about 50 mole percent of the totalinterpolymer.

The carboxyl content of the aforementioned carboxyl containingpolyolefins is preferably in the range of about 3 to 25 mole percent ofthe total carboxyl containing polyolefin although contents of about 1 to50 mole percent can also be employed if desired.

It is preferred to employ random carboxyl containing polyolefinsprepared by the free radical polymerization of an a-olefin with an a,B-ethylenically unsaturated monocarboxylic acid. It is further preferredto employ ethylene as the aolefin and acrylic or methacrylic acid as thea, B-ethylenically unsaturated monocarboxylic acid. If one desires,however, it is also possible to employ block or graft carboxylcontaining polyolefins.

The alkylaminoalkyl acrylates and alkylaminoalkyl methacrylates used inthe present invention to prepare the prepolymer reaction product containabout six to 14 carbon atoms. Specific examples include:dimethylaminoethyl acrylate, diethylaminoethyl acrylate,diethylaminopropyl acrylate, dimethylaminoethyl methacrylate,diethylarninoethyl methacrylate, diethylaminopropyl methacrylate, andthe like.

Representative amino substituted styrenes falling within the purview ofthe general formula given above includes such compounds as o, p orm-amino styrene, N-methylamino styrene, N,N-dimethylamino styrene,dimethylaminomethyl styrenes, dimethylaminoethyl styrenes,diethylaminoethyl styrenes, dimethylaminohexyl styrenes,diethylaminoctyl styrenes, diethylaminodecyl styrenes, vinylbenzytrimethylammonium hydroxide, vinyl phenyl trimethylammoniumhydroxide and the like.

Among the vinyl monomers suitable for copolymerization with theprepolymer reaction product are alkyl acrylates and methacrylatescontaining up to about 18 carbon atoms in the alkyl group. Specificexamples include: methyl acrylate, ethyl acrylate, propyl acrylate,butyl acrylate, hexyl acrylate, 2- ethylhexyl acrylate, dodecylacrylate, hexadecyl acrylate, octadecyl acrylate, methyl methacrylate,ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexylmethacrylate, decyl methacrylate, dodecyl methacrylate, hexadecylmethacrylate, octyldecyl methacrylate, and the like.

Alkyl substituted styrenes suitable for use as the vinyl monomer includep-methylstyrene, p-ethylstyrene, p-isobutylstyrene, m-methylstyrene,m-ethylstyrene, m-isobutylstyrene, and the like.

Vinyl esters suitable for use as the vinyl comonomer include vinylformate, vinyl acetate, vinyl propionate, vinyl butyrate, vinylstearate, and the like.

Vinyl alkyl ethers suitable as comonomers include vinyl methyl ether,vinyl ethyl ether, vinyl propyl ether, vinyl isopropyl ether, vinylbutyl ether, vinyl octadecyl ether, and the like.

The polymer salt compositions of this invention can be prepared by firstneutralizing at least mole percent the carboxyl containing polyolefinwith the amino vinyl monomer to afford a prepolymer. This is preferablyeffected in a common solvent such as a cyclicether as for exampletetrahydrofuran or dioxane. Other solvents which can be used includemixtures of alkanols with aliphatic hydrocarbons or aromatichydrocarbons such as benzene, toluene, xylene, and the like. Thetemperature at which this first step is carried out is not narrowlycritical but depends upon the concentration and solubility of thereactants. A convenient temperature range extends from room temperatureup to the boiling point of the particular solvent used. The salt whicharises as a consequence can be isolated by precipitation with acoagulating solvent as for example a saturated hydrocarbon such ashexene, heptane or the like. However, it has been found more convenientto permit the prepolymer to remain in solution and then proceed with theformation of the vinyl copolymer by copolymerizing one of the vinylmonomers cited above with the prepolymer. The latter step can beaffected with conventional free radical vinyl polymerization initiatorssuch as peroxides, peroxydicarbonates, azo compounds, and the like.Suitable peroxides include benzoyl peroxide, lauroyl peroxide, capryloylperoxide and the like. Exemplary of peroxydicarbonates are dipropylperoxydicarbonate, diisobutyl peroxydicarbonate and the like.Representative azo compounds include: azobisisobutyronitrile,11,11'azodicyclohexanecarbonitrile azobis-a,aazodicyclohexanecarbonitrile, azobis-a,a'-dimethyl valeronitrile,di-methyl-a,a'-azodiisobutyrate and the like. This final polymerizationstep can be affected at temperatures of about 20 to 130 C. dependingupon the decomposition temperature of the initiator chosen and themolecular weight of the product obtained. Pressure is not critical butfor convenience atmospheric pressure are preferred althoughsubatmospheric and superatmospheric pressures can be used if desired.

The polymer salt compositions resulting from the copolymerizationdescribed above can be recovered from the reaction media by evaporationof the solvents or by precipitation with a coagulating solvent byprocedures well known in the art. The products can be obtained asdispersions or as a solid polymer by conventional techniques well knownin the polymer art such as spray dying, centrifugation, ventedextrusion, precipitation with a nonsolvent such as aliphatichydrocarbons and the like.

Adhesive bonding is obtained with the polymer salt compositions of thisinvention by wetting out the substrate with the copolymer composition.In one embodiment it is preferred to heat the polymer salt compositionwhich has previously been pressed into the form of a film to atemperature of about 120 to 200 C. in intimate content with thesubstrate to be bonded at moderate pressures of about 1 to 300 p.s.i.for at least 2 seconds.

Adhesive bonding can also be effected by precoating the substrate to bebonded from a dispersion of the copolymer salt compositions byconventional techniques such as dip coating, brushing, roller coatingand the like, and subsequently heat activating the precoat, whilecontacting the precoated substrates. It is understood that either onesubstrate or both of a pair can be precoated prior to bonding.

As an alternative application one preheated adherend precoated with theadhesive polymeric salt compositions of this invention can be bonded tofoaming polyurethane, vinyl or similar resins. For example, in the caseof polyurethanes they can be formed in situ by foaming adiisocyanate-polyol formulation in contact with a precoated substrateheated to about 75 C. The exotherm generated by the diisocyanatepolyolreaction is sufficient to fuse the resultant polyurethane to theprecoated adherend. Similarly vinyl resins can be melted, foamed withblowing agents, well known in the art, and bonded to preheated,precoated adherends.

Temperature is not narrowly critical and bonding may be effective aboveand below the ranges shown. The method of heat transfer is not criticalbut a minimum pressure is required to ensure adequate surface contactbetween the substrate and the adhesive. Suitable methods of heattransfer include heating by convection (hot air), conduction (laminatingand pressing), radiation (infrared ovens), and the like.

Composite laminates consisting of various combination of polymericpaperlike compositions, cellulosic, polyhydroxyether, metal, magneticmetal oxide, rubber modified styrene polymers, polystyrene, vitreous,vinyl chloride polymer, vinylidene chloride polymer substrates and thelike can be fabricated by in-line techniques well known in the art.

Examples of cellulosic substrates include: wood, plywood, sawdust, cane,bamboo, rattan, paper and the like.

Examples of metal substrates include: aluminum, chromium, cobalt,copper, gold, iron, lead, magnesium, nickel, platinum, silver, tin,titanium, tungsten, vanadium, zinc, and the like as well as alloys suchas alloy steel, galvanized iron, alnico, brass, bronze, carbon steel,cast iron, chromium steel, nichrome, pewter, solder, stainless steel,sterling silver, and the like. These metal substrates can be in the formof powders, granules, whiskers, leaves, foils, sheets, bars, rods, wireand the like. Magnetic metal oxides include those of Fe and Cr.

Included within the definition of vitreous substrates are: glass,fiberglas, ceramics, clays, china, porcelain and the like.

Polyhydroxyetlier substrates are the linear reaction products of adihydric phenol and epichlorohydrin having a molecular weight of greaterthan 25,000 such as those referred to in US. Pat. No. 3,305,528.

The preparation of polyurethanes useful in this invention are disclosedin the textbook Polyurethanes-Chernistry and Technology, LH. Saundersand K. C. Frisch, Interscience Publishers, NY. 19.

The vinyl chloride and vinylidene chloride resins useful in thisinvention are described in Vinyl and Related Compounds by C. E.Schildknecht, John Wiley and Sons, Inc, N.Y.C. 1952.

Polystyrenes and rubber modified styrene polymers are described inStyrene, R. H. Boundy and R. F. Boyer, Reinhold Publishing Corp., N.Y.C.1952, p. 1,226.

The invention is further described by the examples which follows inwhich all parts and percentages are by weight unless otherwisespecified.

EXAMPLE l Into a l-liter round-bottom three-necked flask with a stirrer,thermometer, and nitrogen inlet tube was placed 38.2 g. of an ethyleneacrylic acid copolymer containing 8.3 percent mole acrylic acidcopolymerized therein and having a melt index of dg./min. together with270 cc. of dioxane. This charge was stirred under a nitrogen atmosphereat a temperature of 80 to C. until solution was effected and then 18.4g. of diethylarninoethyl acrylate was added. The resultant solution wasstirred for an additional 15 to 30 minutes after which time 12.7 g. ofmethyl methacrylate and 0.065 g. of azobisisobutyronitrile were added.Then 46 g. of methyl methacrylate and an additional 0.065 g. ofazobisisobutyronitrile in 30 cc. of dioxane were added over a period of30 minutes to one hour at 80 to 90 C. Stirring at 80 to 90 C. wascontinued for an additional 2 hours. A polymer salt composition wasisolated by the addition of the reaction mixture to excess hexane. Thepolymer salt composition which precipitated was compression molded intoplaques at a press temperature of about C. A IO-g. sample of thispolymer salt composition was extracted with acetone in a Soxhletextractor and indicated that 67 percent of the polymer salt compositionwas insoluble and 33 percent soluble in acetone. The soluble fractionwas a copolymer of methyl methacrylate and diethylaminoethyl acrylate(as indicated by its infrared absorption spectrum) which had a reducedviscosity when measured as a 0.2 weight percent solution in chloroformat 30 C. of 0.2. The insoluble fraction was ethylene/acrylic acidcopolymer as indicated by its infrared absorption spectrum.

EXAMPLE 2 The procedure described in Example I with exception that 15.7g. of dimethylaminoethyl methacrylate was substituted for thediethylaminoethyl acrylate. The resultant polymer salt compositioncontained 70 percent acetone insoluble fraction and a 30 percent solublefraction. The'reduced viscosity of the soluble copolymer when measuredas described in Example 1 was 0.2. Films of the polymer salt compositionwere also prepared by compression molding at 150 C.

EXAMPLE 3 The procedure described in Example 1 was followed with theexception that 54 g. of ethyl acrylate was substituted for the methylmethacrylate and 15.7 g. of dimethylaminoethyl methacrylate wassubstituted for diethylaminoethyl acrylate. This polymer saltcomposition consisted of an acetone insoluble fraction of 61 percent andan acetone soluble fraction of 39 percent. The reduced viscosity of thesoluble fraction of the copolymer was 1.0.

EXAMPLE 4 Using the procedure described in Example 1 with the exceptionthat 55.3 g. of ethyl acrylate substituted for the methyl methacrylate.This polymer salt composition had an acetone insoluble fraction of 62percent and an acetone soluble fraction of 38 percent. The reducedviscosity of the soluble fraction of the copolymer was 2.2.

The adhesion of the compositions of this invention was demonstrated witha series of substrates using the polymer salt composition productobtained in Example 2 in film form 2 to mils thick to efiect laminationwith a series of dissimilar substrates. The lamination temperature, thepeel strength of the laminate obtained, and the identities of thevarious substrates are delineated in the table l. Peel strengths weredetermined by peeling back a portion of the film of copolymercomposition product of Example 1 adhering to the respective substrateand then applying a force to this peeled back portion and measuring theforce required to peel the film from the substrate with an lnstronTensile Testing machine. A suitable method for measuring peel strengthis described in ASTM D-903-49. Peel strength data are given in poundsper linear inch (lb./in.) at 2 inch/minute crosshead speed of thelnstron Tensile Testing machine. In examples where the peel strengths oflaminates rather than those of coated single substrates were measured,one of the lamina was peeled back and the peeling force then applied.

l Trademark for fibers of acrylonitrile/vinyl chloride (40/60)copolymer:

2. Plasticized with dioctyl phthalate.

3. Plasticized with polyester plasticizer.

4. Trademark for vinylidene chloride/vinyl chloride copolymera.

5.C -polymerofh dr 1 and r EXAMPLES 5-10 Into a 1-liter round-bottomflask fitted with a stirrer, thermometer, condenser and nitrogen inlettube was charged 38.2 g. of an ethylene acrylic acid copolymercontaining 8.3 mole percent acrylic acid copolymerized therein togetherwith 165 ml. of a 50:50 toluene-butanol mixture. Solution was effectedby stirring at to C. under a nitrogen atmosphere. In six separateexperiments dimethylarninoethyl methacrylate in amounts equal to 15.7g., 12.5 g., 9.45 g., 6.3 g., 3.16 g. and 1.6 g. respectively, wereadded to the flask and stirring continued for 15 minutes at 80 to 90 C.In each experiment 10 g. of methyl methacrylate and 0.1 g. ofazobisisobutyronitrile was added. The nitrogen inlet tube was thenreplaced by a dropping funnel from which 44 g. of methyl methacrylateand 0.1 g. of azobisisobutyronitrile in 35 ml. of toluene-butanol wasgradually added to the flask over a period of 30 minutes. Stirring wascontinued for 2 hours. The polymer salt composition product was isolatedin each example by coagulation in nhexane. Alternatively emulsions ordispersions of these polymer salt composition products were obtained byadding about 200 ml. of methanol to the reaction mixture at about 60 C.followed by cooling to room temperature with stirring.

Laminates of sheets of commercially available polyvinyl chloride resin(plasticized with dioctyl phthalate) and low density polyethylene panelseach bonded to aluminum Q panels were prepared using the polymer saltcompositions obtained in examples 5-10 as the adhesive. The bondingconditions were to C. at 20 to 200 p.s.i. for about 0.5 to 5 minutes.The peel strength values of the laminates thus obtained are presented intable 11:

TABLE II Peel strength, lbs. [linear inch Polyvinyl chloride-Polyethylenealuminum aluminum The use of the polymer salt compositionproduct of Example 2 in films, 10 to 15 mils thick, was alsodemonstrated as an adhesive for the fabrication of laminates of variousmaterials. The laminating condition, temperatures and peel strengthvalues are given in table 111.

rene 4 vinyl resin TABLE 111 Continued Lamination temperature lrnslcelAdhesive 'lmnp., .'-l|l|l1, 'limn/ strength, thickness, lrrnninnlc "(1.psi. min. ll)./in. mils.

om-ll cloth A" 130 84 2.0 0.0

vinyl resin EXAMPLES 1 1-13 Sheets of paperlike olefin polymerCompositions such as those described in US. Pat. No. 3,234,313 andBelgian Pat. Nos. 6,719, 27,600, and 23,693 published respectively onDec. 16, 1964, Feb. 4, 1966 and May 3, 1966 were coated with an emulsionof the polymer salt composition product of Example 9 and dried at 50 C.for 8 to 10 minutes. These precoated sheets were then bonded at 120 to130 C. under a pressure of 40 to 80 p.s.i. for 18-40 seconds to sheetsof polystyrene containing 6 percent mineral oil, 12 percent rubbermodified polystyrene, or unplasticized vinyl chloride resin. The peelstrength of the resultant laminates were 5, 4 and 7 lb./in. respectivelywhen measured 1 hour after lamination. When measured again after 3 daysthese values had increased in each example to greater than 14 lb./in.

It is to be understood that the polymer salt compositions of thisinvention can also be used to provide decorative and/or protectiveoverlays on any of the hereinbefore described substrates. If desiredthese overlays can contain conventional pigments, stabilizers,antioxidants, fillers, and plasticizers well known in the art.

EXAMPLE 14 An emulsion of the polymer salt composition product ofExample 5 was added to panels of Douglas fir plywood and dried. Theresultant coatings were glossy giving the appearance of finished woodand were hard as evidenced by their resistance to scratching with aStarrett scriber under conditions which clearly scored the same uncoatedwood panels.

EXAMPLES 15-20 in a series of experiments an ethylene-acrylic acidcopolymer containing about 18 percent of acrylic acid copolymerizationtherein and having a melt index of about 80 dgJmin. was neutralized withvarying amounts of dimethylaminoethyl methacrylate and thencopolymerized with methyl methacrylate using the method described inExample l. The amounts were chosen to afford ratios of moles ofdimethylaminoethyl methacrylate to moles of carboxyl abbreviated as:

mole DMAEM ,7 7 e2 Q is of 0.1, 0.2, 0.4, 0.6, 0.8 and 1.0. The peelvalues of vinyl-aluminum and polyethylene-aluminum laminates bonded withthese polymer salts were recorded in table IV.

Although the invention has been described in its preferred forms with acertain degree of particularity, it is understood that the presentdisclosure of the preferred forms has been made only by way of exampleand that numerous changes may be resorted to without departing from thespirit and the scope of the invention.

What is claimed is:

1. A reversibly cross-linked, thermoplastic, nonnally solid polymer saltcomposition comprising:

A. about 20 to percent by weight of a prepolymer of a random copolymerof an a-olefin and an a, B-ethylenically unsaturated vmonocarboxylicacid and about 10 to mole percent of said carboxyl groups neutralizedwith an amino vinyl monomer selected from the class consisting ofalkylaminoalkyl acrylates, alkylaminoalkyl methacrylates and aminosubstituted styrenes having the structure CHZCH2 wherein q is an integerhaving values of 0 to l, R is a divalent aliphatic radical having fromone to six carbon atoms, and each of R and R is a monovalent radicalselected from the group consisting of hydrogen and alkyl radicals havingfrom one to six carbon atoms, said prepolymer being copolymerized withB. about 80 to 20 percent by weight of a vinyl monomer selected from theclass consisting of alkyl acrylates, alkyl methacrylates, acrylamide,methacrylamide, styrene, alkyl substituted styrenes, vinyl chloride,vinyl esters containing from about three to 20 carbon atoms and vinylalkyl ethers containing from about three to 30 carbon atoms.

2. The composition claimed inclaim 1 wherein the random copolymer of ana-olefin and an a, B-ethylenically unsaturated monocarboxylic acid is anethylene/acrylic acid copolymer containing from about 2 to 50 molepercent acylic acid copolymerized therein.

3. The composition claimed in claim 2 wherein the amino vinyl monomer isdiethylaminoethyl acrylate and the vinyl monomer is methyl methacrylate.

4. The composition claimed in claim 2 wherein the amino vinyl monomer isdiethylarninoethyl methacrylate and the vinyl monomer is methylmethacrylate.

5. The composition claimed in claim 2 wherein the amino vinyl monomer isdimethylaminoethyl methacrylate and the vinyl monomer is methylmethacrylate.

6. An article comprising a laminate of at least one of the polymer saltcompositions claimed in claim 1 adhesively bonded to substrates selectedfrom the class consisting of metals, vinyl chloride resins, cellulosicmaterials, siliceous materials, vinylidene chloride polymers, paperlikeolefin polymer compositions, polyurethanes, polystyrenes, rubbermodified styrene polymers, and magnetic metal oxides.

- 7. Method for preparing a reversibly cross-linked thermoplastic,normally solid polymer salt composition which comprises the steps of:

a. intimately admixing a random copolymer of an a-olefin and an a,B-ethylenically unsaturated monocarboxylic 1 Ethylene'acrylic acidcopolymer, 18% acrylic acid, M1 80 (lg/min. I Dimethylaminoethylmethacrylate.

3 Methyl methaerylate.

4 Low density polyethylene.

acid having from 2 to 50 mole percent carboxyl .groups copolymerizingabout to 80 percent by weight of the reaction product of (a) with about80 to 20 percent by weight of a vinyl monomer selected from the classconsisting of alkylacrylates, alkylmethacrylates, acrylamide,methacrylamide, styrene, alkyl substituted styrenes, vinyl chloride,vinyl esters containing from about three to 20 carbon atoms and vinylalkyl ethers containing from about three to 30 carbon atoms; and

c. recovering resultant polymer salt composition.

8. The method claimed in claim 7 wherein the random copolymer of ana-olefin and an a, ,B-ethylenically unsaturated monocarboxylic acid isan ethylene acrylic acid copolymer containing from about 2 to 50 percentacrylic acid copolymerized therein.

9. The method claimed in claim 8 wherein the amino vinyl monomer isdiethylaminoethyl acrylate and the vinyl monomer is methyl methacrylate.

10. The method claimed in claim 8 wherein the random copolymer of ana-olefin and an a, B-ethylenically unsaturated monocarboxylic acid is anethylene acrylic acid copolymer having from about 3 to 45 percentacrylic acid copolymerized therein and the amino vinyl monomer isdimethylaminoethyl methacrylate.

l 1. Method for providing protective coatings on a substrate selectedfrom the class consisting of metals, vinyl chloride resins, cellulosicmaterials, siliceous materials, vinylidene chloride polymers, paperlikeolefin polymer compositions, polyurethanes, polystyrenes and rubbermodified styrene polymers which comprises applying a dispersion of areversibly cross-linked, thermoplastic, normally solid polymer saltcomposition comprising:

A. a prepolymer of a random copolymer of an a-olefin and an a,B-ethylenically unsaturated monocarboxylic acid having 2 to 50 molepercent carboxyl groups and about 10 to 100 mole percent of saidcarboxyl groups neutralized with an amino vinyl monomer selected fromthe class consisting of alkylaminoalkyl acrylates, alkylaminoalkylmethacrylates and amino substituted styrenes having the wherein q is aninteger having values of 0 to l, R is an divalent aliphatic radicalhaving from one to six carbon atoms, and each of R, and R is amonovalent radical selected from the group consisting of hydrogen andalkyl radicals having from one to six carbon atoms, said prepolymerbeing copolymerized with B. about to 20 percent by weight of a vinylmonomer selected from the class consisting of alkyl acrylates, alkylmethacrylates, acrylamide, methacrylamide, styrene, alkyl substitutedstyrenes, vinyl chloride, vinyl esters containing from about three to 20carbon atoms and vinyl alkyl ethers containing from about three to 30carbon atoms, to the surface of said substrate, and drying saidsubstrate. 12. Article claims in claim 6 consisting of vinyl chloridepolymer bonded to a wire.

13. Article claimed in claim 12 wherein the wire is copper. 14. Articleclaimed in claim 6 wherein one structure is magnetic iron oxide.

* it a

2. The composition claimed in claim 1 wherein the random copolymer of anAlpha -olefin and an Alpha , Beta -ethylenically unsaturatedmonocarboxylic acid is an ethylene/acrylic acid copolymer containingfrom about 2 to 50 mole percent acylic acid copolymerized therein. 3.The composition claimed in claim 2 wherein the amino vinyl monomer isdiethylaminoethyl acrylate and the vinyl monomer is methyl methacrylate.4. The composition claimed in claim 2 wherein the amino vinyl monomer isdiethylaminoethyl methacrylate and the vinyl monomer is methylmethacrylate.
 5. The composition claimed in claim 2 wherein the aminovinyl monomer is dimethylaminoethyl methacrylate and the vinyl monomeris methyl methacrylate.
 6. An article comprising a laminate of at leastone of the polymer salt compositions claimed in claim 1 adhesivelybonded to substrates selected from the class consisting of metals, vinylchloride resins, cellulosic materials, siliceous materials, vinylidenechloride polymers, paperlike olefin polymer compositions, polyurethanes,polystyrenes, rubber modified styrene polymers, and magnetic metaloxides.
 7. Method for preparing a reversibly cross-linked,thermoplastic, normally solid polymer salt composition which comprisesthe steps of: a. intimately admixing a random copolymer of an Alpha-olefin and an Alpha , Beta -ethylenically unsaturated monocarboxylicacid having from 2 to 50 mole percent carboxyl groups therein with anamino vinyl monomer selected from the class consisting ofalkylaminoalkyl acrylates, alkylaminoalkyl methacrylates, and aminosubstituted styrenes; and b. copolymerizing about 20 to 80 percent byweight of the reaction product of (a) with about 80 to 20 percent byweight of a vinyl monomer selected from the class consisting ofalkylacrylates, alkylmethacrylates, acrylamide, methacrylamide, styrene,alkyl substituted styrenes, vinyl chloride, vinyl esters containing fromabout three to 20 carbon atoms and vinyl alkyl ethers containing fromabout three to 30 carbon atoms; and c. recovering resultant polymer saltcomposition.
 8. The method claimed in claim 7 wherein the randomcopolymer of an Alpha -olefin and an Alpha , Beta -ethylenicallyunsaturated monocarboxylic acid is an ethylene acrylic acid copolymercontaining from about 2 to 50 percent acrylic acid copolymerizedtherein.
 9. The method claimed in claim 8 wherein the amino vinylmonomer is diethylaminoethyl acrylate and the vinyl monomer is methylmethacrylate.
 10. The method claimed in claim 8 wherein the randomcopolymer of an Alpha -olefin and an Alpha , Beta -ethylenicallyunsaturated monocarboxylic acid is an ethylene acrylic acid copolymerhaving from about 3 to 45 percent acrylic acid copolymerized therein andthe amino vinyl monomer is dimethylaminoethyl methacrylate.
 11. Methodfor providing protective coatings on a substrate selected from the classconsisting of metals, vinyl chloride resins, ceLlulosic materials,siliceous materials, vinylidene chloride polymers, paperlike olefinpolymer compositions, polyurethanes, polystyrenes and rubber modifiedstyrene polymers which comprises applying a dispersion of a reversiblycross-linked, thermoplastic, normally solid polymer salt compositioncomprising: A. a prepolymer of a random copolymer of an Alpha -olefinand an Alpha , Beta -ethylenically unsaturated monocarboxylic acidhaving 2 to 50 mole percent carboxyl groups and about 10 to 100 molepercent of said carboxyl groups neutralized with an amino vinyl monomerselected from the class consisting of alkylaminoalkyl acrylates,alkylaminoalkyl methacrylates and amino substituted styrenes having thestructure wherein q is an integer having values of 0 to 1, R is andivalent aliphatic radical having from one to six carbon atoms, and eachof R1 and R2 is a monovalent radical selected from the group consistingof hydrogen and alkyl radicals having from one to six carbon atoms, saidprepolymer being copolymerized with B. about 80 to 20 percent by weightof a vinyl monomer selected from the class consisting of alkylacrylates, alkyl methacrylates, acrylamide, methacrylamide, styrene,alkyl substituted styrenes, vinyl chloride, vinyl esters containing fromabout three to 20 carbon atoms and vinyl alkyl ethers containing fromabout three to 30 carbon atoms, to the surface of said substrate, anddrying said substrate.
 12. Article claims in claim 6 consisting of vinylchloride polymer bonded to a wire.
 13. Article claimed in claim 12wherein the wire is copper.
 14. Article claimed in claim 6 wherein onesubstrate is magnetic iron oxide.